DE4228476A1 - Obtaining tocopherol and sterol - Google Patents
Obtaining tocopherol and sterolInfo
- Publication number
- DE4228476A1 DE4228476A1 DE4228476A DE4228476A DE4228476A1 DE 4228476 A1 DE4228476 A1 DE 4228476A1 DE 4228476 A DE4228476 A DE 4228476A DE 4228476 A DE4228476 A DE 4228476A DE 4228476 A1 DE4228476 A1 DE 4228476A1
- Authority
- DE
- Germany
- Prior art keywords
- sterol
- mixture
- tocopherol
- fatty acids
- lower alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229930182558 Sterol Natural products 0.000 title claims abstract description 51
- 235000003702 sterols Nutrition 0.000 title claims abstract description 51
- 229930003799 tocopherol Natural products 0.000 title claims abstract description 50
- 239000011732 tocopherol Substances 0.000 title claims abstract description 50
- 150000003432 sterols Chemical class 0.000 title claims abstract description 45
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 title claims abstract description 41
- 235000010384 tocopherol Nutrition 0.000 title claims abstract description 39
- 229960001295 tocopherol Drugs 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003925 fat Substances 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 235000021588 free fatty acids Nutrition 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 235000010469 Glycine max Nutrition 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 244000068988 Glycine max Species 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000003784 tall oil Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 235000011187 glycerol Nutrition 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 235000019149 tocopherols Nutrition 0.000 description 11
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 11
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 9
- 229930003427 Vitamin E Natural products 0.000 description 8
- -1 steroid alcohols Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000008158 vegetable oil Substances 0.000 description 8
- 235000019165 vitamin E Nutrition 0.000 description 8
- 239000011709 vitamin E Substances 0.000 description 8
- 229940046009 vitamin E Drugs 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 235000019197 fats Nutrition 0.000 description 6
- 125000005456 glyceride group Chemical group 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 235000012424 soybean oil Nutrition 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000003549 soybean oil Substances 0.000 description 5
- 150000003626 triacylglycerols Chemical class 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000000199 molecular distillation Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 150000003611 tocopherol derivatives Chemical class 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 2
- DFUSDJMZWQVQSF-XLGIIRLISA-N (2r)-2-methyl-2-[(4r,8r)-4,8,12-trimethyltridecyl]-3,4-dihydrochromen-6-ol Chemical compound OC1=CC=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 DFUSDJMZWQVQSF-XLGIIRLISA-N 0.000 description 2
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 235000012000 cholesterol Nutrition 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000007700 distillative separation Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003505 terpenes Chemical group 0.000 description 2
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- KZJWDPNRJALLNS-VPUBHVLGSA-N (-)-beta-Sitosterol Natural products O[C@@H]1CC=2[C@@](C)([C@@H]3[C@H]([C@H]4[C@@](C)([C@H]([C@H](CC[C@@H](C(C)C)CC)C)CC4)CC3)CC=2)CC1 KZJWDPNRJALLNS-VPUBHVLGSA-N 0.000 description 1
- CSVWWLUMXNHWSU-UHFFFAOYSA-N (22E)-(24xi)-24-ethyl-5alpha-cholest-22-en-3beta-ol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(CC)C(C)C)C1(C)CC2 CSVWWLUMXNHWSU-UHFFFAOYSA-N 0.000 description 1
- RQOCXCFLRBRBCS-UHFFFAOYSA-N (22E)-cholesta-5,7,22-trien-3beta-ol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CCC(C)C)CCC33)C)C3=CC=C21 RQOCXCFLRBRBCS-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GJJVAFUKOBZPCB-UHFFFAOYSA-N 2-methyl-2-(4,8,12-trimethyltrideca-3,7,11-trienyl)-3,4-dihydrochromen-6-ol Chemical compound OC1=CC=C2OC(CCC=C(C)CCC=C(C)CCC=C(C)C)(C)CCC2=C1 GJJVAFUKOBZPCB-UHFFFAOYSA-N 0.000 description 1
- KLEXDBGYSOIREE-UHFFFAOYSA-N 24xi-n-propylcholesterol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CCC)C(C)C)C1(C)CC2 KLEXDBGYSOIREE-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 235000019737 Animal fat Nutrition 0.000 description 1
- DSEKYWAQQVUQTP-UHFFFAOYSA-N Cerin Natural products CC12CCC3(C)C4CC(C)(C)CCC4(C)CCC3(C)C2CCC2(C)C1CC(O)C(=O)C2C DSEKYWAQQVUQTP-UHFFFAOYSA-N 0.000 description 1
- LPZCCMIISIBREI-MTFRKTCUSA-N Citrostadienol Natural products CC=C(CC[C@@H](C)[C@H]1CC[C@H]2C3=CC[C@H]4[C@H](C)[C@@H](O)CC[C@]4(C)[C@H]3CC[C@]12C)C(C)C LPZCCMIISIBREI-MTFRKTCUSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- ARVGMISWLZPBCH-UHFFFAOYSA-N Dehydro-beta-sitosterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)CCC(CC)C(C)C)CCC33)C)C3=CC=C21 ARVGMISWLZPBCH-UHFFFAOYSA-N 0.000 description 1
- DNVPQKQSNYMLRS-NXVQYWJNSA-N Ergosterol Natural products CC(C)[C@@H](C)C=C[C@H](C)[C@H]1CC[C@H]2C3=CC=C4C[C@@H](O)CC[C@]4(C)[C@@H]3CC[C@]12C DNVPQKQSNYMLRS-NXVQYWJNSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001026509 Kata Species 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 241000158147 Sator Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000004100 adrenal gland Anatomy 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- 210000001557 animal structure Anatomy 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- MJVXAPPOFPTTCA-UHFFFAOYSA-N beta-Sistosterol Natural products CCC(CCC(C)C1CCC2C3CC=C4C(C)C(O)CCC4(C)C3CCC12C)C(C)C MJVXAPPOFPTTCA-UHFFFAOYSA-N 0.000 description 1
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- GZCJJOLJSBCUNR-UHFFFAOYSA-N chroman-6-ol Chemical class O1CCCC2=CC(O)=CC=C21 GZCJJOLJSBCUNR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000012716 cod liver oil Nutrition 0.000 description 1
- 239000003026 cod liver oil Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000003246 corticosteroid Substances 0.000 description 1
- 229960001334 corticosteroids Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- DNVPQKQSNYMLRS-SOWFXMKYSA-N ergosterol Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H](CC[C@]3([C@H]([C@H](C)/C=C/[C@@H](C)C(C)C)CC[C@H]33)C)C3=CC=C21 DNVPQKQSNYMLRS-SOWFXMKYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 235000002378 plant sterols Nutrition 0.000 description 1
- 239000000186 progesterone Substances 0.000 description 1
- 229960003387 progesterone Drugs 0.000 description 1
- 239000000583 progesterone congener Substances 0.000 description 1
- 229940095055 progestogen systemic hormonal contraceptives Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 description 1
- 235000015500 sitosterol Nutrition 0.000 description 1
- 229950005143 sitosterol Drugs 0.000 description 1
- NLQLSVXGSXCXFE-UHFFFAOYSA-N sitosterol Natural products CC=C(/CCC(C)C1CC2C3=CCC4C(C)C(O)CCC4(C)C3CCC2(C)C1)C(C)C NLQLSVXGSXCXFE-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 210000000278 spinal cord Anatomy 0.000 description 1
- 229930193551 sterin Natural products 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 1
- 235000016831 stigmasterol Nutrition 0.000 description 1
- 229940032091 stigmasterol Drugs 0.000 description 1
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003802 tocotrienol Natural products 0.000 description 1
- 239000011731 tocotrienol Substances 0.000 description 1
- 235000019148 tocotrienols Nutrition 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3544—Organic compounds containing hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
- C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Gewinnen von Tocopherol, gegebe nenfalls auch von Sterol, aus einem Tocopherol, Fette und/oder Fettderi vate, insbesondere Fettsäuren, und gegebenenfalls Sterol und/oder Sterol derivate enthaltenden Gemisch.The invention relates to a process for the recovery of tocopherol also from sterol, from a tocopherol, fats and / or Fettderi vate, especially fatty acids, and optionally sterol and / or sterol mixture containing derivatives.
Tocopherolverbindungen sind in vielen pflanzlichen und tierischen Ölen enthalten und werden auch als Vitamin E bezeichnet. Die Bezeichnung Vita min E bezieht sich auf die physiologische Wirkung dieser Nahrungsmittelin haltsstoffe.Tocopherol compounds are found in many vegetable and animal oils contain and are also called vitamin E. The term Vita min E refers to the physiological effects of these foods ingredients.
Es sind 8 natürlich vorkommende Substanzen mit Vitamin-E-Wirkung bekannt. Sie sind Derivate des 6-Chromanols und gehören zu 2 Gruppen von Verbin dungen. Die erste Gruppe leitet sich vom Tocol ab und trägt eine gesättig te isoprenoide Seitenkette mit 16 C-Atomen. Zu dieser Gruppe gehören al pha-, beta-, gamma- und delta-Tocopherol. Die Verbindungen unterscheiden sich im Methylierungsgrad am Benzolkern des Tocols. Alpha-Tocopherol ist dabei die Substanz mit der stärksten biologischen Vitamin-E-Wirkung und der größten technischen und wirtschaftlichen Bedeutung. Es ist das domi nierende Tocopherol im menschlichen und tierischen Gewebe.Eight naturally occurring substances with a vitamin E effect are known. They are derivatives of 6-chromanol and belong to 2 groups of verbin fertilize. The first group is derived from the tocol and carries one saturated te isoprenoid side chain with 16 carbon atoms. This group includes al pha, beta, gamma and delta tocopherol. The connections differ the degree of methylation at the benzene nucleus of the tocol. Is alpha tocopherol the substance with the strongest biological vitamin E effect and of the greatest technical and economic importance. It is the domi tocopherol in human and animal tissues.
Die zweite Gruppe von Substanzen mit Vitamin-E-Wirkung sind die Derivate des Tocotrienols. Sie unterscheiden sich von den anderen Tocopherol-Homo logen durch die ungesättigte isoprenoide Seitenkette mit 16 C-Atomen. Die natürlich vorkommenden Toco-Enole zeigen ebenfalls eine Vitamin-E-Wirkung und werden üblicherweise zusammen mit den gesättigten Tocopherol-Homologen aus ihren natürlichen Quellen bei der Gewinnung von Vitamin E isoliert. Die Bezeichnung "Tocopherol" soll in dieser Anmeldung auch diese Tocophe rol-Homologen, also alle Substanzen mit Vitamin-E-Wirkung, umfassen. The second group of substances with a vitamin E effect are the derivatives of tocotrienol. They differ from the other tocopherol homo lied through the unsaturated isoprenoid side chain with 16 carbon atoms. The naturally occurring toco-enols also show a vitamin E effect and are commonly used along with the saturated tocopherol homologs isolated from their natural sources in the production of vitamin E. The term "tocopherol" is also intended to refer to these tocopher in this application rol homologs, i.e. all substances with a vitamin E effect.
Die Tocopherole finden wegen ihrer oxidationshemmenden Eigenschaften An wendung im Nahrungsmittel- und im kosmetisch-pharmazeutischen Bereich so wie als Zusatz in auf natürlichen Ölen basierenden Anstrichfarben.The tocopherols are due to their anti-oxidant properties application in the food and cosmetic-pharmaceutical sector as an additive in paints based on natural oils.
Die Bezeichnung "Sterol" umfaßt in dieser Anmeldung die Sterole, die auch Sterine genannt werden. Beide Bezeichnungen "Sterol" und "Sterin" werden in dieser Patentanmeldung als gleichbedeutend benutzt. Die Sterole sind 1-wertige sekundäre Steroidalkohole mit 27 bis 30 Kohlenstoffatomen, die die Grundstruktur des Gonans besitzen. Das Kohlenstoffatom 3 des Gonans trägt die Hydroxylgruppe. Die strukturellen Unterschiede der einzelnen bisher in der Natur gefundenen Sterole bestehen im Auftreten von Doppel bindungen innerhalb des Ringsystems, im Eintritt von Substituenten an be vorzugten Stellen und in der Konstitution der Seitenkette, die am Kohlen stoffatom 17 des Gonans verankert ist.The term "sterol" in this application includes the sterols, which also Be called sterols. Both terms "Sterol" and "Sterin" will be used as equivalent in this patent application. The sterols are 1-valent secondary steroid alcohols with 27 to 30 carbon atoms, the have the basic structure of the gonan. The carbon atom 3 of the gonan carries the hydroxyl group. The structural differences of each Sterols found so far in nature consist of double occurrences bonds within the ring system, in the entry of substituents on be preferred places and in the constitution of the side chain that is on the coals Substance atom 17 of the gonan is anchored.
Der wichtigste Vertreter der Sterole ist das Cholesterin, das frei oder verestert in tierischen Organen und Flüssigkeiten, insbesondere im Gehirn, im Rückenmark, den Nebennieren, im Lebertran und im Wollfett vorkommt. Cholesterin gehört zu den sogenannten Zoosterinen, mit denen man die in tierischen fetten enthaltenen Sterine bezeichnet. Die pflanzlichen Sterine werden Phytosterine genannt. Die wichtigsten Vertreter sind Ergosterin, Stigmasterin, Campesterin und Sitosterin. Die Sterine oder Sterole sind wertvolle Ausgangsstoffe in der Synthese von Pharmazeutika, insbesondere von Steroidhormonen, z. B. Corticosteroiden und Gestagenen. Zum Beispiel kann Stigmasterin leicht zum Progesteron umgewandelt werden.The main representative of sterols is cholesterol, which is free or esterified in animal organs and fluids, especially in the brain, occurs in the spinal cord, adrenal glands, cod liver oil and wool fat. Cholesterol is one of the so-called zoosterols, with which one gets the in called animal fat containing sterols. The plant sterols are called phytosterols. The main representatives are ergosterol, Stigmaster, campester and sitosterol. The sterols or sterols are valuable starting materials in the synthesis of pharmaceuticals, in particular of steroid hormones, e.g. B. Corticosteroids and progestogens. For example stigmasterol can easily be converted to progesterone.
Die Ausgangsgemische zum Gewinnen von Tocopherol und Sterol können eine Vielzahl von pflanzlichen und tierischen Substanzen sein. Die höchsten Konzentrationen von Tocopherol finden sich in pflanzlichen Ölen wie Wei zenkeim-, Mais-, Soja- und Palmkernöl. Tocopherol findet sich jedoch auch in anderen Pflanzenölen, zum Beispiel Safloröl, Erdnußöl, Baumwollkeimöl, Sonnenblumenöl, Rapsöl, Palmöl und anderen Pflanzenölen.The starting mixtures for tocopherol and sterol recovery can be one Variety of vegetable and animal substances. The highest Concentrations of tocopherol are found in vegetable oils such as white Zen germ, corn, soy and palm kernel oil. However, tocopherol is also found in other vegetable oils, e.g. safflower oil, peanut oil, cotton germ oil, Sunflower oil, rapeseed oil, palm oil and other vegetable oils.
Die natürlichen Pflanzenöle enthalten nur geringe Mengen an Tocopherol. Eine Aufkonzentrierung ist für gewerbliche Anwendungen erwünscht. Verun reinigungen sollen ferner abgetrennt werden, um die antioxidierende Wir kung und die Vitamin-E-Aktivität zu verstärken. Die wichtigsten natürli chen Quellen für Tocopherol sind daher nicht die Pflanzenöle selbst, son dern die bei der Desodorierung pflanzlicher und tierischer Öle anfallenden Wasserdampfdestillate, die auch Dämpferdestillate genannt werden. Hier fallen die Tocopherole zwar konzentriert, aber gemischt mit Sterol und Sterolestern, freien Fettsäuren sowie Triglyceriden an. Besonders interes sant ist das Destillat aus der Desodorierung von Sojaöl. Auf die besondere Eignung von Sojaöl als Quelle für Tocopherole wird zum Beispiel in Fat Sci. Technol., 91. Jahrgang, 1989, S. 39 bis 41, in einem Vergleich der Desodorierungsdestillate von Soja- und Rapsöl hingewiesen. Das Sojadämp ferdestillat enthält etwa 10 Ma % Mischtocopherole und in gleicher Größen ordnung Sterole, die in überwiegender Menge in ihrer Esterform vorliegen.The natural vegetable oils contain only small amounts of tocopherol. Concentration is desirable for commercial applications. Verun Purifications should also be separated to the antioxidant we kung and to increase the vitamin E activity. The most important of course Chen sources of tocopherol are therefore not the vegetable oils themselves, but those that occur during the deodorization of vegetable and animal oils Steam distillates, which are also called steam distillates. Here the tocopherols fall concentrated, but mixed with sterol and Sterol esters, free fatty acids and triglycerides. Particularly interesting The distillate from the deodorization of soybean oil is sant. The special one Suitability of soybean oil as a source of tocopherols is described, for example, in Fat Sci. Technol., 91st year, 1989, pp. 39 to 41, in a comparison of the Deodorizing distillates from soybean and rapeseed oil pointed out. The soybean steamer ferdestillat contains about 10% mixed tocopherols and in the same sizes order sterols which are predominantly present in their ester form.
Zum Aufkonzentrieren von Tocopherol sind unterschiedliche Verfahren be kannt, nämlich Veresterung, Verseifung und fraktionierende Ex traktion. So werden Tocopherol-Konzentrate nach der DE 31 26 110 A1 aus Nebenprodukten der Desodorierung von Ölen und fetten dadurch gewonnen, daß die in diesen enthaltenen freien Fettsäuren durch Anlagerung eines Alko hols verestert oder die freien Fettsäuren aus den Destillaten abdestil liert werden, woraufhin diese Produkte einer Hydrierung und anschließend einer Lösungsmittelfraktionierung zur Extraktion der Tocopherole unterwor fen werden. Aus dem gleichen Dokument ist ein anderes Verfahren zum Auf konzentrieren von Tocopherol bekannt. Hier werden die Desodorierungsde stillate einer Umesterung mit Methanol unterworfen und die Fettsäuremethylester abdestilliert. Der Rückstand wird durch Molekulardestillation aufkonzentriert.There are different methods for concentrating tocopherol knows, namely esterification, saponification and fractionating ex traction. So tocopherol concentrates according to DE 31 26 110 A1 By-products of the deodorization of oils and fats obtained in that the free fatty acids contained in them by the addition of an alcohol hols esterified or the free fatty acids from the distillates Liert, whereupon these products a hydrogenation and then a solvent fractionation to extract the tocopherols be opened. Another method of opening is from the same document concentrate of tocopherol known. Here are the deodorants Stillate subjected to a transesterification with methanol and the fatty acid methyl esters distilled off. The residue is obtained by molecular distillation concentrated.
Ein weiteres, aus der EP 171 009 A2 bekanntes Verfahren bringt das Toco pherol-haltige Material mit einer ausreichenden Menge eines polaren or ganischen Lösungsmittels in Kontakt, das die Tocopherole, aber nicht die Verunreinigungen löst. Die mit Tocopherol angereicherte polare Phase wird abgetrennt und aus dieser das Tocopherol gewonnen.Another method known from EP 171 009 A2 is the Toco material containing pherol with a sufficient amount of a polar or ganischen solvent in contact, which the tocopherols, but not the Removes impurities. The polar phase enriched with tocopherol becomes separated and the tocopherol obtained from this.
Ferner ist die Abtrennung der Tocopherole durch Adsorption an basischen Anionenaustauschern bekannt. Diese Variante ist möglich, wenn das Gemisch keine oder nur wenig Fettsäuren enthält. Die Sterole, Glyceride und andere neutrale oder basische Substanzen werden nicht adsorbiert (Ullmanns En zyklopädie der technischen Chemie, 4. Auflage, Band 23, 1984, S. 645).Furthermore, the separation of the tocopherols by adsorption on basic Anion exchangers known. This variant is possible if the mixture contains little or no fatty acids. The sterols, glycerides and others neutral or basic substances are not adsorbed (Ullmanns En Zyklopadie der Technische Chemie, 4th edition, volume 23, 1984, p. 645).
ferner ist die fraktionierte Kristallisation zur Abtrennung der Sterole von den Tocopherolen nach der Aufkonzentrierung bekannt. Dabei geht Toco pherol in Lösung und Sterol kristallisiert aus. Auch eine destillative Trennung von Tocopherol und Sterol ist möglich, aber dabei wird Sterol, zumindest zum Teil, zerstört. Nach einer schonenden Trennung von Tocophe rol und Sterol werden also 2 Wertprodukte erhalten.Furthermore, fractional crystallization is used to separate the sterols known from the tocopherols after concentration. Toco does it pherol crystallizes in solution and sterol. Also a distillative Separation of tocopherol and sterol is possible, but sterol, at least partially, destroyed. After a gentle separation from Tocophe rol and sterol will thus receive 2 valuable products.
Die bekannten Verfahren zum Gewinnen von Tocopherol und gegebenenfalls auch von Sterol haben unterschiedliche Nachteile.The known methods for the recovery of tocopherol and optionally Sterol also have different disadvantages.
Die Extraktionsverfahren müssen oft auf das Ausgangsgemisch abgestimmt werden, da die darin enthaltenen Begleitstoffe die Extraktion stark beein flussen und die gewünschten Wertprodukte Tocopherol und Sterol bei glei chem Extraktionsverfahren und unterschiedlichen Ausgangsgemischen nicht immer in die gewünschte Phase gehen. Die bekannten Extraktionsverfahren verwenden außerdem gesundheitlich bedenkliche Lösungsmittel.The extraction processes often have to be matched to the starting mixture be, because the accompanying substances strongly influence the extraction flow and the desired value products tocopherol and sterol at glei chem extraction process and different starting mixtures not always go to the desired phase. The known extraction processes also use solvents that are harmful to health.
Ionenaustauscher wirken spezifisch auf das Ausgangsmaterial, erfordern eine gute Vorreinigung des Gemisches und ermöglichen keine simultane Auf konzentrierung von Tocopherol und Sterol.Ion exchangers have a specific effect on the starting material a good pre-cleaning of the mixture and do not allow simultaneous opening concentration of tocopherol and sterol.
Tocopherol wird in einer in dem Dokument DE 31 26 110 A1 beschriebenen Variante nach einer Veresterung der freien Fettsäuren mittels mehrwertiger Alkohole einer Molekulardestillation oder einer Wasserdampfdestillation unterworfen, um ein Destillat mit einem hohen Tocopherolgehalt zu erhal ten. Der Verfahrensschritt der Molekulardestillation ist jedoch im tech nischen Maßstab unwirtschaftlich, und die Wasserdampfdestillation führt zu einer höheren thermischen Belastung, die die Sterole zumindest teilweise zerstört. Im letzteren fall kann also nur das thermisch stabilere Toco pherol in guter Ausbeute gewonnen werden.Tocopherol is described in one in document DE 31 26 110 A1 Variant after an esterification of the free fatty acids using polyvalent ones Alcohols of a molecular distillation or a steam distillation subjected to obtain a distillate with a high tocopherol content The process step of molecular distillation is, however, in tech African scale uneconomical, and steam distillation leads to a higher thermal load, which the sterols at least partially destroyed. In the latter case, only the thermally more stable toco can pherol can be obtained in good yield.
Der Erfindung liegt daher die Aufgabe zugrunde, ein für viele unterschied liche Ausgangsgemische anwendbares Verfahrens zum Gewinnen von Tocopherol und gegebenenfalls auch von Sterol bereitzustellen, das ohne toxikologisch und ökologisch bedenkliche Lösungsmittel arbeitet, thermisch schonend vor geht, gute Ausbeuten erreicht und in wirtschaftlicher Weise im technischen Maßstab durchführbar ist. Die gleichzeitige Gewinnung von Tocopherol und Sterol soll außerdem möglich sein.The invention is therefore based on the object, a difference for many Liche starting mixtures applicable method for the recovery of tocopherol and possibly also to provide sterol that is toxicologically free and ecologically questionable solvent works, thermally gentle goes, good yields achieved and economical in technical Scale is feasible. The simultaneous production of tocopherol and Sterol should also be possible.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß manThis object is achieved in that
- 1) im Gemisch vorhandende freie Fettsäuren mit einem niederen Alkohol, bevorzugt Methanol, verestert,1) free fatty acids present in the mixture with a lower alcohol, preferably methanol, esterified,
- 2) danach das Gemisch mit dem niederen Alkohol in Gegenwart eines basi schen Katalysators umestert,2) then the mixture with the lower alcohol in the presence of a base transesterified catalyst
- 3) nach der Umesterung den überschüssigen niederen Alkohol aus dem Reaktionsgemisch abdestilliert,3) after the transesterification, the excess lower alcohol from the Distilled reaction mixture,
- 4) den Umesterungskatalysator sowie gegebenenfalls das enthaltene Gly cerin, insbesondere durch Waschen, abtrennt,4) the transesterification catalyst and optionally the Gly contained separates cerin, in particular by washing,
- 5) den Fettsäurealkylester, insbesondere nach Abtrennung des Umesterungs katalysators, aus dem Gemisch abdestilliert und5) the fatty acid alkyl ester, especially after the transesterification has been separated off catalyst, distilled from the mixture and
- 6) gewünschtenfalls Tocopherol und Sterol in an sich bekannter Weise trennt.6) if desired, tocopherol and sterol in a manner known per se separates.
Die im Ausgangsgemisch enthaltenen freien Fettsäuren werden in einem ersten Schritt mit einem niederen Alkohol zu Fettsäurealkylester, insbe sondere Fettsäuremethylester, umgesetzt, um eine Verseifungsreaktion mit dem im nächsten Schritt eingesetzten Umesterungskatalysator auszu schließen. Bei Gemischen ohne freie Fettsäuren kann dieser erste Schritt entfallen. Im nachfolgenden Verfahrensschritt, der Umesterung, werden die Sterol-Fettsäure-Ester zu Sterol und Fettsäuremethylester umgesetzt. Die Partial- und Triglyceride reagieren zu Glycerin und Fettsäuremethylester. Das im Gemisch enthaltene Tocopherol reagiert nicht. In manchen fällen liegen nicht nur Tocopherole, sondern auch Tocopherol-Ester im Ausgangsge misch vor, zum Beispiel im Sojaöl-Dämpferdestillat mit 0,5 Ma %. Die Ester werden in diesem Schritt in Tocopherole umgesetzt. Für den nächsten Ver fahrensschritt, die Abdestillation des überschüssigen niederen Alkohols, ist es besonders vorteilhaft, wenn in den vorangegangenen Stufen ein mög lichst kurzkettiger Alkohol eingesetzt worden ist, insbesondere Methanol. Auf diese Weise läßt sich die thermische Belastung niedrig halten. Vor der Abdestillation der Fettsäurealkylester empfiehlt sich neben der Abtrennung des Glycerins, das in der Umesterungsstufe aus gegebenenfalls vorhandenen Triglyceriden entstanden ist, auch die Entfernung des Umesterungskatalysa tors. Der Katalysator liegt im wesentlichen in Form von Alkaliseife vor, die bei der Destillation stören und zum Beispiel zur Erhöhung des Siede punktes führen könnte. Nach der Abtrennung der Fettsäurealkylester erhält man ein hochaufkonzentriertes Tocopherol-Sterol-Gemisch, aus dem Tocophe rol und Sterol voneinander in an sich bekannter Weise, zum Beispiel durch Kristallisation getrennt werden können.The free fatty acids contained in the starting mixture are combined in one first step with a lower alcohol to fatty acid alkyl esters, esp special fatty acid methyl ester, implemented to have a saponification reaction the transesterification catalyst used in the next step shut down. For mixtures without free fatty acids, this first step can omitted. In the subsequent process step, the transesterification, the Sterol fatty acid esters converted to sterol and fatty acid methyl ester. The Partial and triglycerides react to glycerin and fatty acid methyl ester. The tocopherol contained in the mixture does not react. In some cases not only tocopherols but also tocopherol esters are in the starting ge pre-mix, for example in soybean oil steam distillate with 0.5% by mass. The esters are converted into tocopherols in this step. For the next ver step, the distillation of the excess lower alcohol, it is particularly advantageous if a possible in the previous stages Lich short-chain alcohol has been used, especially methanol. In this way, the thermal load can be kept low. Before the Distillation of the fatty acid alkyl esters is recommended in addition to the separation of the glycerol which may be present in the transesterification stage Triglycerides has formed, including the removal of the transesterification catalyst tors. The catalyst is essentially in the form of alkali soap, which interfere with the distillation and for example to increase the boiling point point could lead. After separation of the fatty acid alkyl ester is obtained a highly concentrated tocopherol-sterol mixture, from the tocophe rol and sterol from one another in a manner known per se, for example by Crystallization can be separated.
Ein großer Vorteil des erfindungsgemäßen Verfahrens liegt in der Vielsei tigkeit der Anwendung auf unterschiedliche, Tocopherol und gegebenenfalls auch Sterol enthaltende Gemische. Insbesondere ist es aber vorteilhaft, wenn man von Sojaöl-Dämpferdestillat ausgeht. Dieses wird durch Wasser dampfdestillation des rohen Sojaöls als erste Stufe des Desodoriervor ganges gewonnen. Das Destillat enthält etwa 20% Sterol, 8% Tocopherol, 20% freie Fettsäuren und als Hauptbestandteil Triglyceride (Ullmann, a.a.O.).A great advantage of the method according to the invention lies in the variety activity of application to different, tocopherol and optionally also mixtures containing sterol. In particular, however, it is advantageous if you start from soybean oil steam distillate. This is caused by water Steam distillation of raw soybean oil as the first step in the deodorization process won. The distillate contains about 20% sterol, 8% tocopherol, 20% free fatty acids and triglycerides as the main component (Ullmann, a.a.O.).
Aber auch Dämpferdestillate anderer Öle lassen sich mit dem Verfahren verarbeiten, zum Beispiel Rapsöl-Destillate.But damper distillates of other oils can also be made with the process process, for example rapeseed oil distillates.
Das Verfahren ist jedoch nicht auf Dämpfer-Destillate pflanzlicher Öle und fette beschränkt. Es läßt sich auch vorteilhaft auf Tallöl anwenden. Tall öl ist eines der wirtschaftlich wichtigsten Nebenprodukte des Cellulose- Sulfat-Verfahrens bei der Papierherstellung. Es wird durch Ansäuern des bei diesem Verfahren anfallenden Natriumsalz-Gemisches von Harz- und Fett säuren erhalten. Tallöl ist ein natürliches Gemisch aus Harzsäuren vom Typ der Abietinsäure, gesättigten und ungesättigten Fettsäuren sowie Fettsäureestern und Unverseifbarem. Das Unverseifbare enthält neben höheren Alko holen und Kohlenwasserstoffen auch Sterole.However, the process is not based on vegetable oils and steam distillates fat limited. It can also be used advantageously on tall oil. Tall oil is one of the economically most important by-products of cellulose Sulphate process in papermaking. It is acidified by the sodium salt mixture of resin and fat obtained in this process get acids. Tall oil is a natural mixture of resin acids of the type abietic acid, saturated and unsaturated fatty acids and fatty acid esters and unsaponifiable. The unsaponifiable contains higher alcohol fetch and hydrocarbons also sterols.
Auch andere, Tocopherol-enthaltende Gemische lassen sich mit dem erfin dungsgemäßen Verfahren aufarbeiten, zum Beispiel der bei der Rapsöl-Me thylester-Herstellung anfallende Rückstand, der ebenfalls Sterole und Sterolester enthält.Other tocopherol-containing mixtures can also be made with the inventions Work up procedures according to the invention, for example that of rapeseed oil me residue produced by the ethyl ester, which is also sterols and Contains sterol esters.
In einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens ver estert man die Fettsäuren in Gegenwart eines, insbesondere in einem Festbettreaktor vorliegenden, stark sauren Ionenaustauschers bei Temperaturen von 60 bis 100°C, insbesondere von 65 bis 70°C. Vorteilhaft und überra schend war der deutlich geringere Verlust von Tocopherol durch die Lös lichkeit in Methanol als bei einer destillativen Abtrennung der Fettsäuren. Bei der Veresterung der Fettsäuren liegt das Verhältnis der Volumen ströme zwischen Dämpferdestillat und niederem Alkohol zwischen 1,1 und 1,7 und vorzugsweise bei 1,4. Die Verweilzeit im Festbettreaktor beträgt 1 bis 2, vorzugsweise 1,6 Stunden. Diese Angabe bezieht sich auf das tatsächlich vorhandene freie Volumen. Bei der Veresterung werden an den aktiven Zen tren des stark sauren Ionenaustauschers die im Gemisch vorhandenen Fettsäuren zu Fettsäurealkylester umgesetzt.In a preferred embodiment of the method according to the invention esters the fatty acids in the presence of a reactor, in particular in a fixed bed reactor present, strongly acidic ion exchanger at temperatures from 60 to 100 ° C, in particular from 65 to 70 ° C. Advantageous and surprising the main reason was the significantly lower loss of tocopherol due to the solution in methanol than with a distillative separation of the fatty acids. The esterification of the fatty acids is the ratio of the volumes flows between steamer distillate and lower alcohol between 1.1 and 1.7 and preferably at 1.4. The residence time in the fixed bed reactor is 1 to 2, preferably 1.6 hours. This statement actually refers to that available free volume. During the esterification, active zen of the strongly acidic ion exchanger are the fatty acids present in the mixture converted to fatty acid alkyl esters.
Im Anschluß an die Reaktion wird der überschüssige niedere Alkohol, also in der Regel Methanol, in einem Phasenabscheider abgetrennt. Der Alkohol enthält außerdem den überwiegenden Teil des bei der Veresterung entstan denen Wassers.Following the reaction, the excess lower alcohol, ie usually methanol, separated in a phase separator. The alcohol also contains the major part of the esterification which water.
Nach der Umesterung und der Entfernung des Überschußalkohols aus dem Re aktionsgemisch wird der Katalysator und das eventuell vorhandene Glycerin aus dem Gemisch entfernt. Vorher wird vorzugsweise der Katalysator durch Ansäuern mit einer anorganischen Säure neutralisiert.After the transesterification and removal of the excess alcohol from the Re The catalyst and any glycerin that may be present become a mixture of actions removed from the mixture. Before this, the catalyst is preferably passed through Acidified neutralized with an inorganic acid.
Im folgenden wird die Erfindung anhand von Ausführungsbeispielen näher erläutert, ohne daß eine Beschränkung auf diese Beispiele vorgenommen wer den soll.In the following, the invention will be explained in more detail using exemplary embodiments explained, without being limited to these examples that should.
Sojadämpferdestillat mit einer Säurezahl von 70 wurde mit einem Volumen strom von 0,094 l/h zusammen mit 0,067 l/h Methanol in eine 0,3 m lange Glassäule, aufgeschüttet mit Katalysator, nämlich mit einem stark sauren, makroporösen Ionenaustauscherharz (Lewatit K 2631), gefördert. Der Durch messer der Säule betrug 0,07 m. Das Gemisch wurde in einem Glasbehälter nach einer Verweilzeit von 1,6 h aufgefangen und dekantiert. Eine an schließende Eindampfung, um das Methanol/Wassergemisch von der Fettphase zu trennen, erfolgte unter Vakuum. Eine abschließend bestimmte Säurezahl ergab einen Wert von 1,3. Das entsprach einem Umsatz von 98%, bei ver nachlässigbarem Verlust an Tocopherol. Das Material ist somit für den nachfolgenden Umesterungsschritt entsäuert worden.Soybean steam distillate with an acid number of 70 was volume flow of 0.094 l / h together with 0.067 l / h methanol in a 0.3 m long Glass column, filled with catalyst, namely with a strongly acidic macroporous ion exchange resin (Lewatit K 2631), promoted. The through The column diameter was 0.07 m. The mixture was placed in a glass container collected and decanted after a residence time of 1.6 h. One on closing evaporation to remove the methanol / water mixture from the fat phase to separate was done under vacuum. A final acid number gave a value of 1.3. That corresponded to a turnover of 98%, with ver negligible loss of tocopherol. The material is therefore for the subsequent transesterification step has been deacidified.
Das im ersten Schritt entsäuerte Sojadämpferdestillat mit einer Säurezahl von etwa 1 wurde in einem Rührreaktor mit Methanol und dem basischen Ka talysator in Kontakt gebracht. Die Reaktionstemperatur lag dabei zwischen 60 und 90°C, vorzugsweise bei 65°C. Bezogen auf das eingesetzte Sojadämp ferdestillat wurden 40-80% Methanol (vorzugsweise 50-60%) und 0,8- 1,5% Katalysator (vorzugsweise 1%) eingesetzt. Als Katalysator wurde vorzugsweise Natriummethylat verwendet. Möglich sind auch andere basische Katalysatoren, wie zum Beispiel Natrium-, Kalium und Lithiumhydroxid, etc. Die Reaktionszeit betrug bei 65°C ca. 2 h. Nach der Umesterung waren die Sterolester zu mindestens 90% und die Glyceride zu mindestens 95% umge setzt.The deacidified soybean steam distillate with an acid number in the first step of about 1 was in a stirred reactor with methanol and the basic Ka brought into contact. The reaction temperature was between 60 and 90 ° C, preferably at 65 ° C. In relation to the soy steam used Ferdestillat 40-80% methanol (preferably 50-60%) and 0.8- 1.5% catalyst (preferably 1%) is used. As a catalyst preferably sodium methylate used. Other basic ones are also possible Catalysts such as sodium, potassium and lithium hydroxide, etc. The reaction time was approximately 2 hours at 65 ° C. After the transesterification they were At least 90% of sterol esters and at least 95% of glycerides puts.
2,8 kg entsäuertes Sojadämpferdestillat mit einer Säurezahl von 1,9 wurde mit 1,4 kg Methanol, in das vorher 192 g 30%iges methanolisches Natrium methylat gelöst wurde, in Kontakt gebracht. Das Gemisch wurde unter stän digem Rühren auf 650 C erwärmt und 2 h bei dieser Temperatur gehalten. Um Tocopherolverluste zu vermeiden, wurde eine Stickstoffatmosphäre überla gert.2.8 kg of deacidified soybean steam distillate with an acid number of 1.9 was with 1.4 kg of methanol, in the previously 192 g of 30% methanolic sodium methylate was dissolved, brought into contact. The mixture was under dig stirring heated to 650 C and held at this temperature for 2 h. Around To avoid loss of tocopherol, a nitrogen atmosphere was left over device.
Das Ausgangsgemisch enthielt rund 6% freie Sterole, nach Umesterung wurde nach Abzug des Methanolanteiles 16% ermittelt. Der anfängliche Glycerid anteil von 25% sank auf 1,2% ab. 90% der Glyceride waren Monoglyceride. Triglyceride waren nicht mehr nachweisbar.The starting mixture contained around 6% free sterols, after transesterification after deducting the methanol content 16% determined. The initial glyceride the share of 25% fell to 1.2%. 90% of the glycerides were monoglycerides. Triglycerides were no longer detectable.
In Anschluß an die Umesterung wurde das überschüssige Methanol aus dem Reaktionsgemisch bei einer Temperatur von 90°C und 100 mbar abdestil liert.Following the transesterification, the excess methanol was removed from the Distill the reaction mixture at a temperature of 90 ° C and 100 mbar liert.
Das entmethanolisierte Reaktionsgemisch enthielt den eingesetzten Kataly sator hauptsächlich in Form der Alkaliseife. Um den Katalysator aus dem Dämpferdestillat zu entfernen, wurde 2,2 kg entmethanolisiertes Sojadämp ferdestillat mit 148 g 3%iger Salzsäure angesäuert und mit 1,1 kg Wasser gewaschen. Im Dekanter wurden beide Phasen separiert.The demethanolized reaction mixture contained the catalyst used sator mainly in the form of alkali soap. To the catalyst from the To remove steamer distillate was 2.2 kg of demethanolized soy steamer Ferdestillat acidified with 148 g of 3% hydrochloric acid and with 1.1 kg of water washed. Both phases were separated in the decanter.
Nach einer Destillation des gebildeten Methylesters aus dem Produkt von Beispiel 4 wurde ein Gemisch erhalten, das als Hauptkomponenten 40 Ma % freie Sterole und 30 Ma % Tocopherole enthielt.After distillation of the methyl ester formed from the product of Example 4 a mixture was obtained, the main components of which were 40% by mass Contained free sterols and 30% tocopherols.
Claims (4)
- 1) im Gemisch vorhandene freie Fettsäuren mit einem niederen Alkohol, bevorzugt Methanol, verestert,
- 2) danach das Gemisch mit dem niederen Alkohol in Gegenwart eines basischen Katalysator umestert,
- 3) nach der Umesterung den überschüssigen niederen Alkohol aus dem Reaktionsgemisch abdestilliert,
- 4) den Umesterungskatalysator sowie das gegebenenfalls ent haltene Glycerin, insbesondere durch Waschen, abtrennt,
- 5) den Fettsäurealkylester, insbesondere nach Abtrennung des Umesterungskatalysators, aus dem Gemisch abdestilliert und
- 6) gewünschtenfalls Tocopherol und Sterol in an sich bekann ter Weise trennt.
- 1) esterified free fatty acids present in the mixture with a lower alcohol, preferably methanol,
- 2) then the mixture is transesterified with the lower alcohol in the presence of a basic catalyst,
- 3) after the transesterification, the excess lower alcohol is distilled off from the reaction mixture,
- 4) the transesterification catalyst and any glycerol which may be present are separated off, in particular by washing,
- 5) the fatty acid alkyl ester, in particular after removal of the transesterification catalyst, is distilled off from the mixture and
- 6) if desired, separates tocopherol and sterol in a manner known per se.
Priority Applications (12)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4228476A DE4228476C2 (en) | 1992-08-27 | 1992-08-27 | Process for the recovery of tocopherol and / or sterol |
AT93919091T ATE163416T1 (en) | 1992-08-27 | 1993-08-18 | EXTRACTION OF TOCOPHEROL AND STEROL |
PCT/EP1993/002207 WO1994005650A1 (en) | 1992-08-27 | 1993-08-18 | Isolation of tocopherol and sterol |
JP50679994A JP3746292B2 (en) | 1992-08-27 | 1993-08-18 | Tocopherol and sterol recovery |
EP93919091A EP0656894B2 (en) | 1992-08-27 | 1993-08-18 | Isolation of tocopherol and sterol |
DK93919091T DK0656894T4 (en) | 1992-08-27 | 1993-08-18 | Extraction of tocopherol and sterol |
ES93919091T ES2112427T5 (en) | 1992-08-27 | 1993-08-18 | OBTAINING TOCOPHEROL AND STEROL. |
US08/387,933 US5627289A (en) | 1992-08-27 | 1993-08-18 | Recovery of tocopherol and sterol from tocopherol and sterol containing mixtures of fats and fat derivatives |
DE59308185T DE59308185D1 (en) | 1992-08-27 | 1993-08-18 | PRODUCTION OF TOCOPHEROL AND STEROL |
CA002143441A CA2143441C (en) | 1992-08-27 | 1993-08-18 | Recovery of tocopherol and sterol |
BR9306967A BR9306967A (en) | 1992-08-27 | 1993-08-18 | Obtaining tocopherol and sterol |
MYPI93001694A MY111793A (en) | 1992-08-27 | 1993-08-24 | Recovery of tocopherol and sterol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4228476A DE4228476C2 (en) | 1992-08-27 | 1992-08-27 | Process for the recovery of tocopherol and / or sterol |
Publications (2)
Publication Number | Publication Date |
---|---|
DE4228476A1 true DE4228476A1 (en) | 1994-03-03 |
DE4228476C2 DE4228476C2 (en) | 2002-05-02 |
Family
ID=6466542
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE4228476A Expired - Fee Related DE4228476C2 (en) | 1992-08-27 | 1992-08-27 | Process for the recovery of tocopherol and / or sterol |
DE59308185T Expired - Fee Related DE59308185D1 (en) | 1992-08-27 | 1993-08-18 | PRODUCTION OF TOCOPHEROL AND STEROL |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE59308185T Expired - Fee Related DE59308185D1 (en) | 1992-08-27 | 1993-08-18 | PRODUCTION OF TOCOPHEROL AND STEROL |
Country Status (11)
Country | Link |
---|---|
US (1) | US5627289A (en) |
EP (1) | EP0656894B2 (en) |
JP (1) | JP3746292B2 (en) |
AT (1) | ATE163416T1 (en) |
BR (1) | BR9306967A (en) |
CA (1) | CA2143441C (en) |
DE (2) | DE4228476C2 (en) |
DK (1) | DK0656894T4 (en) |
ES (1) | ES2112427T5 (en) |
MY (1) | MY111793A (en) |
WO (1) | WO1994005650A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0712399A1 (en) * | 1993-08-06 | 1996-05-22 | Henkel Corporation | Recovery of tocopherols |
EP0866789A1 (en) * | 1995-12-13 | 1998-09-30 | Henkel Corporation | Recovery of tocopherols |
WO2000047570A1 (en) * | 1999-02-13 | 2000-08-17 | Cognis Deutschland Gmbh | Method for producing phytosterols |
WO2002046340A1 (en) * | 2000-12-04 | 2002-06-13 | Dr. Frische Gmbh | Method for the production of fatty acid esters |
US6956125B2 (en) | 2000-08-07 | 2005-10-18 | Cognis Deutschland Gmbh & Co. Kg | Processes for producing sterols from fatty acid production residues |
WO2015197155A1 (en) | 2014-06-24 | 2015-12-30 | Weylchem Wiesbaden Gmbh | Method for obtaining vitamin e, sterols and/or terpenes from oily or fatty mixtures of biological origin |
US9884837B2 (en) | 2010-11-03 | 2018-02-06 | Verbio Vereinigte Bioenergie Ag | Method for obtaining phytosterols and/or tocopherols from residue of a distillation of the esters of vegetable oils, preferably from distillation residue from a transesterification of vegetable oils |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2787714B1 (en) | 1998-12-23 | 2003-01-31 | Pharmascience Lab | USE OF UNSAPONIFIABLE VEGETABLE OILS FOR THE PREPARATION OF A MEDICAMENT STIMULATING THE EXPRESSION OF TGF-BETA OR THE EXPRESSION OF THE PAI-1 INHIBITOR OF THE PLASMINOGEN ACTIVATOR |
DE19916034C1 (en) * | 1999-04-09 | 2000-08-03 | Cognis Deutschland Gmbh | Isolation of phytosterols following methyl esterification of rape seed or soya fatty acids comprises crystallization from 25 - 75 wt. % methanol, useful as hypocholesterolemic agents in drugs and foods |
MY127954A (en) | 1999-11-04 | 2007-01-31 | Malaysian Palm Oil Board | A method of chromatographic isolation for non-glyceride components |
US6414166B1 (en) | 1999-12-29 | 2002-07-02 | National Science Council | Process for preparing tocopherol concentrates |
DE10038457B4 (en) * | 2000-08-07 | 2008-09-25 | Cognis Ip Management Gmbh | Process for the production of sterols and tocopherols |
DE10038456A1 (en) * | 2000-08-07 | 2002-02-21 | Cognis Deutschland Gmbh | Process for the production of sterols |
ATE391135T1 (en) | 2001-09-07 | 2008-04-15 | Raisio Staest Oy | METHOD FOR ISOLATION OF STEROLS AND/OR WAXY ALCOHOLS FROM TALL OIL PRODUCTS |
ATE463477T1 (en) * | 2003-02-21 | 2010-04-15 | Cognis Ip Man Gmbh | METHOD FOR OBTAINING FATTY ACID ALKYLESTERS, RESIN ACIDS AND STEROLS FROM CRUDE TALL OIL |
US7293047B2 (en) * | 2003-10-23 | 2007-11-06 | Microsoft Corporation | Synchronization view |
WO2008008810A2 (en) * | 2006-07-11 | 2008-01-17 | Wiley Organics, Inc. | Process for isolating phytosterols and tocopherols from deodorizer distillate |
US20080282606A1 (en) * | 2007-04-16 | 2008-11-20 | Plaza John P | System and process for producing biodiesel |
EP2252626B1 (en) * | 2008-03-10 | 2014-07-23 | SunPine AB | Recovery of phytosterols from residual vegetable oil streams |
WO2011033346A1 (en) * | 2009-09-15 | 2011-03-24 | Council Of Scientific & Industrial Research | A process for conversion of low cost and high ffa oils to biodiesel |
EP2697348B1 (en) | 2011-04-14 | 2015-10-21 | Alfa Laval Corporate AB | A process for autocatalytic esterification of fatty acids |
WO2013184070A1 (en) * | 2012-06-05 | 2013-12-12 | Agency For Science, Technology And Research | A drusen lesion image detection system |
US10030211B2 (en) * | 2013-08-30 | 2018-07-24 | Inventure Renewables, Inc. | Methods for the separation or purification of vitamin E, tocopherols and tocotrienols from lipid mixtures |
CN103467432B (en) * | 2013-09-16 | 2016-08-17 | 四川省仁德制药有限公司 | A kind of method extracting vitamin E from deodorizer distillate of idesia polycarpa oil |
JP6426192B2 (en) | 2013-09-30 | 2018-11-21 | エイエイケイ、アクチボラグ (ピーユービーエル)Aak Ab (Publ) | Triterpene ester concentration |
SG11201703858YA (en) | 2014-11-14 | 2017-06-29 | Basf Plant Science Co Gmbh | Materials and methods for increasing the tocopherol content in seed oil |
CN105693683B (en) * | 2014-11-28 | 2018-11-27 | 丰益(上海)生物技术研发中心有限公司 | The method of vitamin E removing plasticiser |
MY193786A (en) | 2015-01-12 | 2022-10-27 | Ho Sue San David | Recovery of tocopherols/tocotrienols, carotenoids, glycerols, sterols and fatty acid esters from crude vegetable oil and the process thereof |
MY176376A (en) * | 2015-02-06 | 2020-08-04 | Ho Sue San David | Recovery of tocopherols/tocotrienols, glycerine, sterols and fatty acid esters from vegetable oil distillate and the process thereof |
JP6548087B2 (en) * | 2015-05-18 | 2019-07-24 | 国立大学法人東北大学 | Selective separation of vitamin E |
CN108033938B (en) * | 2017-11-21 | 2021-06-15 | 合肥工业大学 | Method for extracting tocopherol from tea oil deodorized distillate by combining acidic ionic liquid catalytic esterification and column chromatography |
CA3146079A1 (en) | 2019-09-27 | 2021-04-01 | Valerie Eychenne | Process for the production and purification of sterols |
CN114450386A (en) | 2019-09-27 | 2022-05-06 | 巴斯夫欧洲公司 | Process for the production of sterols and/or tocopherols and recovery of by-products |
EP4034618A1 (en) * | 2019-09-27 | 2022-08-03 | Basf Se | Process for the purification of phytosterol |
SE545114C2 (en) * | 2021-06-24 | 2023-04-04 | Stora Enso Oyj | Fractionation of crude tall oil |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1170126A (en) * | 1954-09-23 | 1959-01-09 | Eastman Kodak Co | Process for obtaining tocopherol concentrates from deodorization sludge and products obtained |
US3335154A (en) * | 1963-06-04 | 1967-08-08 | Eastman Kodak Co | Separation of tocopherols and sterols from deodorizer sludge and the like |
DE3126110A1 (en) * | 1980-07-04 | 1982-04-01 | The Nisshin Oil Mills, Ltd., Tokyo | Process for obtaining tocopherol concentrates |
JPS6042495A (en) * | 1983-08-17 | 1985-03-06 | 日清製油株式会社 | Methylesterification of oil and fat deodorant distillate |
GB8418274D0 (en) * | 1984-07-18 | 1984-08-22 | Inst Penyelidikan Minyak Kelap | Carboxylic acid esterification |
DE3582904D1 (en) * | 1984-08-02 | 1991-06-27 | Henkel Corp | CLEANING TOCOPHEROLS BY EXTRACTION. |
DE3501761A1 (en) * | 1985-01-21 | 1986-07-24 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRE-Esterification OF FREE FATTY ACIDS IN RAW FATS AND / OR OILS |
DE3615029A1 (en) * | 1985-05-06 | 1986-11-06 | Henkel Corp., Minneapolis, Minn. | METHANOL EXTRACTION OF TOCOPHEROL |
GB8729232D0 (en) * | 1987-12-15 | 1988-01-27 | Palm Oil Research Inst Of Mala | Recovery of carotenoids tocopherols tocotrienols & sterols from esterified palm oil |
EP0333472B1 (en) * | 1988-03-16 | 1997-10-08 | PALM OIL RESEARCH & DEVELOPMENT BOARD | Production of high concentration tocopherols and tocotrienols from palm oil by-products |
-
1992
- 1992-08-27 DE DE4228476A patent/DE4228476C2/en not_active Expired - Fee Related
-
1993
- 1993-08-18 AT AT93919091T patent/ATE163416T1/en not_active IP Right Cessation
- 1993-08-18 DE DE59308185T patent/DE59308185D1/en not_active Expired - Fee Related
- 1993-08-18 EP EP93919091A patent/EP0656894B2/en not_active Expired - Lifetime
- 1993-08-18 CA CA002143441A patent/CA2143441C/en not_active Expired - Fee Related
- 1993-08-18 WO PCT/EP1993/002207 patent/WO1994005650A1/en active IP Right Grant
- 1993-08-18 JP JP50679994A patent/JP3746292B2/en not_active Expired - Fee Related
- 1993-08-18 US US08/387,933 patent/US5627289A/en not_active Expired - Lifetime
- 1993-08-18 DK DK93919091T patent/DK0656894T4/en active
- 1993-08-18 ES ES93919091T patent/ES2112427T5/en not_active Expired - Lifetime
- 1993-08-18 BR BR9306967A patent/BR9306967A/en not_active Application Discontinuation
- 1993-08-24 MY MYPI93001694A patent/MY111793A/en unknown
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0712399A1 (en) * | 1993-08-06 | 1996-05-22 | Henkel Corporation | Recovery of tocopherols |
EP0712399A4 (en) * | 1993-08-06 | 1996-05-29 | ||
EP0992500A2 (en) * | 1993-08-06 | 2000-04-12 | Henkel Corporation | Recovery of tocopherols |
EP0992500A3 (en) * | 1993-08-06 | 2000-04-26 | Henkel Corporation | Recovery of tocopherols |
EP0866789A1 (en) * | 1995-12-13 | 1998-09-30 | Henkel Corporation | Recovery of tocopherols |
EP0866789A4 (en) * | 1995-12-13 | 1999-04-07 | Henkel Corp | Recovery of tocopherols |
WO2000047570A1 (en) * | 1999-02-13 | 2000-08-17 | Cognis Deutschland Gmbh | Method for producing phytosterols |
US6979743B1 (en) | 1999-02-13 | 2005-12-27 | Cognis Deutschland Gmbh & Co. Kg | Processes for preparing phytosterols and substantially citrostadienol-free phytosterols prepared thereby |
US6956125B2 (en) | 2000-08-07 | 2005-10-18 | Cognis Deutschland Gmbh & Co. Kg | Processes for producing sterols from fatty acid production residues |
WO2002046340A1 (en) * | 2000-12-04 | 2002-06-13 | Dr. Frische Gmbh | Method for the production of fatty acid esters |
US6960673B2 (en) | 2000-12-04 | 2005-11-01 | Westfalia Separator Ag | Method for pretreating crude oils and raw fats for the production of fatty acid esters |
US7109363B2 (en) | 2000-12-04 | 2006-09-19 | Westfalia Separator Ag | Method for the production of fatty acid esters |
US9884837B2 (en) | 2010-11-03 | 2018-02-06 | Verbio Vereinigte Bioenergie Ag | Method for obtaining phytosterols and/or tocopherols from residue of a distillation of the esters of vegetable oils, preferably from distillation residue from a transesterification of vegetable oils |
WO2015197155A1 (en) | 2014-06-24 | 2015-12-30 | Weylchem Wiesbaden Gmbh | Method for obtaining vitamin e, sterols and/or terpenes from oily or fatty mixtures of biological origin |
US10150749B2 (en) | 2014-06-24 | 2018-12-11 | Weylchem Wiesbaden Gmbh | Method for obtaining vitamin E, sterols and/or terpenes from oily or fatty mixtures of biological origin |
Also Published As
Publication number | Publication date |
---|---|
MY111793A (en) | 2001-01-31 |
US5627289A (en) | 1997-05-06 |
EP0656894B1 (en) | 1998-02-25 |
EP0656894A1 (en) | 1995-06-14 |
ES2112427T5 (en) | 2003-01-01 |
CA2143441A1 (en) | 1994-03-17 |
ATE163416T1 (en) | 1998-03-15 |
JPH08500598A (en) | 1996-01-23 |
BR9306967A (en) | 1999-01-12 |
JP3746292B2 (en) | 2006-02-15 |
EP0656894B2 (en) | 2002-06-12 |
DE59308185D1 (en) | 1998-04-02 |
DK0656894T3 (en) | 1998-09-23 |
DE4228476C2 (en) | 2002-05-02 |
DK0656894T4 (en) | 2002-07-15 |
WO1994005650A1 (en) | 1994-03-17 |
ES2112427T3 (en) | 1998-04-01 |
CA2143441C (en) | 2004-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE4228476C2 (en) | Process for the recovery of tocopherol and / or sterol | |
DE69434277T2 (en) | Recovery of tocopherols | |
EP0610742B1 (en) | Process for obtaining tocopherols and sterols from natural sources | |
DE69837623T2 (en) | STEROLESTER AS FOOD ADDITIVE | |
DE69722210T2 (en) | METHOD FOR PRODUCING A MIXTURE OF STERIN ESTERS | |
DE60304407T2 (en) | Extraction of vitamin E, phytosterols and squalene from palm oil | |
DE69910152T2 (en) | Use of phytosterol and / or phytostanol esters | |
DE2248921C3 (en) | Process for the production of a mixture of vegetable and animal oils or fats and fatty acid ester esters | |
EP3160953B1 (en) | Process for obtaining vitamin e, sterols and/or terpenes from oleaginous compositions of biological origin | |
DE60033904T2 (en) | Chromatographic method to isolate squalene, steroids, vitamin E and carotenoids. | |
DE60117869T2 (en) | PROCESS FOR THE PRODUCTION OF TOCOTRIENOLS | |
DE10038457B4 (en) | Process for the production of sterols and tocopherols | |
EP1179536B1 (en) | Process for the isolation of sterols from the residues of fatty-acid or methyl-ester production | |
DE19916034C1 (en) | Isolation of phytosterols following methyl esterification of rape seed or soya fatty acids comprises crystallization from 25 - 75 wt. % methanol, useful as hypocholesterolemic agents in drugs and foods | |
EP0819116B1 (en) | Process for obtaining carotene from palm oil | |
EP2635592B1 (en) | Method for obtaining phytosterols and/or tocopherols from residue of a distillation of the esters of vegetable oils, preferably from distillation residue from a transesterification of vegetable oils | |
DE19652522C2 (en) | Process for the production of tocopherols and / or sterols | |
DE2236930A1 (en) | PROCESS FOR THE PRODUCTION OF DESMOSTEROL | |
EP3052603B2 (en) | Enrichment of triterpene esters | |
DE60022215T2 (en) | PROCESS FOR THE PREPARATION OF PHYTOSTEROLS BY FLUID IN A SOLVENT CONTAINING WATER / ALCOHOL | |
US10793539B2 (en) | Process for the preparation of tocols and squalene | |
EP3287014B1 (en) | Process for producing a phytosterol-phystostanol composition | |
CN110720556A (en) | Apocynum venetum sterol extract and preparation method and application thereof | |
EP0316729A2 (en) | Process for the enrichment of tocopherols in natural springs | |
DE1053733B (en) | Process for the production of tocopherol concentrates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
8110 | Request for examination paragraph 44 | ||
8127 | New person/name/address of the applicant |
Owner name: COGNIS DEUTSCHLAND GMBH, 40589 DUESSELDORF, DE |
|
D2 | Grant after examination | ||
8327 | Change in the person/name/address of the patent owner |
Owner name: COGNIS DEUTSCHLAND GMBH & CO. KG, 40589 DUESSELDOR |
|
8364 | No opposition during term of opposition | ||
8327 | Change in the person/name/address of the patent owner |
Owner name: COGNIS IP MANAGEMENT GMBH, 40589 DUESSELDORF, DE |
|
8339 | Ceased/non-payment of the annual fee |